Organic electroluminescent materials and devices
Provided is an organometallic complex including a ligand LA having a structure represented by one of the following formulas and coordiated to Ir.
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This application is a continuation of U.S. patent application Ser. No. 15/948,059, filed Apr. 9, 2018, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/488,406, filed Apr. 21, 2017, and to U.S. Provisional Application No. 62/488,107, filed Apr. 21, 2017, the entire contents of which are incorporated herein by reference.
FIELDThe present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
BACKGROUNDOpto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
SUMMARYA compound is disclosed which comprises a first ligand LA Selected from the group consisting of:
In Formulas I, II, and III, ring A is a 5- or 6-membered carbocyclic or heterocyclic ring; Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus; Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron; each of R1, R2, and RA independently represents none to a maximum possible number of substitutions; each of R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; any two substitutions in R1, R2, and RA are optionally joined or fused into a ring; the ligand LA is coordinated to a metal M; and M is optionally coordinated to other ligands. If LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand. If LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.
An organic light emitting device (OLED) is also disclosed where the OLED comprises: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, the organic layer comprising the inventive compound.
A consumer product comprising the OLED is also disclosed.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-1”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.
The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.
The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to five heteroatoms. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be unsubstituted or may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R1 is mono-substituted, then one R1 must be other than H. Similarly, where R1 is di-substituted, then two of R1 must be other than H. Similarly, where R1 is unsubstituted, R1 is hydrogen for all available positions. The maximum number of substitutions possible in a structure will depend on the number of atoms with available valencies.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
A compound is disclosed which comprises a first ligand LA selected from the group consisting of:
In Formulas I, II, and III, ring A is a 5- or 6-membered carbocyclic or heterocyclic ring; Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus; Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron; each of R1, R2, and RA independently represents none to a maximum possible number of substitutions; each of R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; any two substitutions in R1, R2, and RA are optionally joined or fused into a ring; the ligand LA is coordinated to a metal M; and M is optionally coordinated to other ligands. If LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand. If LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.
In some embodiments of the compound, each of R1, R2, and RA is independently selected from hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.
In some embodiments of the compound, M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some embodiments, M is Ir or Pt.
In some embodiments of the compound, the compound is homoleptic. In some embodiments, the compound is heteroleptic.
In some embodiments of the compound, ring A is a 6-membered aromatic ring. In some embodiments, ring A is a 5-membered aromatic ring.
In some embodiments of the compound, Z1 is an anionic coordinating atom selected from the group consisting of C, N, and O. In some embodiments, the anionic coordinating carbon is an sp2 carbon atom of a ring selected from the group consisting of benzene, pyridine, furan, thiophene, and pyrrole; wherein the anionic coordinating nitrogen is an sp2 nitrogen atom of an N-heterocyclic ring selected from the group consisting of imidazole, benzoimidazole, pyrazole, and triazole; and wherein the anionic oxygen atom is the oxygen atom from a carboxylic acid or ether.
In some embodiments of the compound, Z1 is a neutral coordinating atom selected from the group consisting of C, P, and N. In some embodiments, the neutral carbon is the neutral carbene carbon of an N-heterocyclic carbene; wherein the neutral phosphorus is the phosphorus atom of a trisubstituted phosphine; and wherein the neutral nitrogen is an sp2 nitrogen atom of an N-heterocyclic ring selected from the group consisting of pyridine, imidazole, benzoimidazole, pyrazole, and triazole.
In some embodiments of the compound, Z6 is nitrogen. In some embodiments, Z6 is oxygen or sulfur. In some embodiments, Z6 is CRR′, PR, or BR; wherein R and R′ are independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and wherein any adjacent substitutions in R and R′ are optionally joined or fused into a ring. In some embodiments, R and R′ are independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.
In some embodiments of the compound, the first ligand LA selected from the group consisting of:
wherein R1′ and R2′ have the same definition as R1 and R2; and wherein X1 to X8 are each independently carbon or nitrogen. In some embodiments, X1 to X8 are each carbon. In some embodiments, at least one of X1 to X8 is nitrogen. In some embodiments, one of X1 to X8 is nitrogen, the remaining of X1 to X8 is carbon. In some embodiments, each ring having X1 to X8 has no more than one nitrogen.
In some embodiments of the compound, the first ligand LA is Selected from the group consisting of:
wherein Y is selected from the group consisting of O, S, Se, and NRD; wherein X1 to X20 are each independently selected from the group consisting of carbon and nitrogen; wherein R1′, R2′, RA′, and RD each independently represents from none to a maximum possible number of substitutions; wherein each of R1′, R2′, RA′, and RD is independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and wherein any two adjacent substituents are optionally joined to form into a ring.
In some embodiments of the compound, the first ligand LA is Selected from the group consisting of:
In some embodiments of the compound, the compound has a formula of M(LA)x(LB)y(LC)z; wherein LB and LC are each a bidentate ligand; and wherein x is 1, 2, or 3; y is 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M. In some embodiments, the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other.
In some embodiments, the compound has a formula of Pt(LA)(LB), wherein LA and LB can be same or different. In some embodiments, LA and LB are connected to form a tetradentate ligand. In some embodiments, LA and LB are connected at two places to form a macrocyclic tetradentate ligand.
In some embodiments of the compound having the formula M(LA)x(LB)y(LC)z, LB and LC are each independently selected from the group consisting of:
wherein each Y1 to Y13 are independently selected from the group consisting of carbon and nitrogen; wherein Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRfRR, SiReRf, and GeReRf; wherein Re and Rf are optionally fused or joined to form a ring; wherein each Ra, Rb, Rc, and Rd may independently represent from mono substitution to the maximum possible number of substitution, or no substitution; wherein each Ra, Rb, Rc, Rd, Re and Rf is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents of Ra, Rb, Rc, and Rd are optionally fused or joined to form a ring or form a multidentate ligand.
In some embodiments of the compound having the formula M(LA)x(LB)y(LC)z, LB and LC are each independently selected from the group consisting of:
In some embodiments of the compound where the first ligand LA is selected from the group consisting of LA1 to LA206, the compound is selected from the group consisting of Compound Ax having the formula Ir(LAi)2(LCj);
wherein x is an integer defined by x=1260i+j−1260; wherein i is an integer from 1 to 206, and j is an integer from 1 to 1260; and
wherein LCj is selected from the group consisting of LC1 through LC1260 that are based on a structure of Formula X,
in which R3, R4, and R5 are defined as:
wherein RD1 to RD81 has the following structures:
In some embodiments of the compound where the first ligand LA is selected from the group consisting of LA1 to LA206, the compound is selected from the group consisting of Compound By having the formula Ir(LAi)(LBk)2; where y is an integer defined by y=460+k−460; i is an integer from 1 to 206, k is an integer from 1 to 460; and where LBk has the following structures:
In some embodiments of the compound, the compound has one of the following formulas:
wherein R1′ and R2′ have the same definition as R1 and R2; and wherein X1 to X8, Z7 and Z8 are each independently carbon or nitrogen; wherein RB, and RC each independently represents none to a maximum possible number of substitutions; wherein m1, m2 and m3 are each independently an integer of 0 or 1;
when m2 is 0, each m1 and m3 is 1;
when m2 is 1, each m1 and m3 are each independently 0 or 1;
when m1 is 0, L1 is not present;
when m2 is 0, L2 is not present;
when m3 is 0, L3 is not present;
wherein L1, L2, and L3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, and combinations thereof;
wherein RB, RC, R, and R′ are each independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof;
wherein any two substitutions are optionally joined or fused into a ring;
wherein Q1 and Q2 are each independently a direct bond or oxygen;
wherein when any of Z7 and Z8 is nitrogen, the Q1 and Q2 attached thereto is a direct bond; and wherein M is Pt or Pd. In some embodiments, M is Pt. In some embodiments, each Q1 and Q2 is a direct bond. In some embodiments, one of Q1 and Q2 is oxygen, and the other one of Q1 and Q2 is direct bond. In some embodiments, one of Z7 and Z8 is carbon, and the other one of Z7 and Z8 is nitrogen. In some embodiments, one of Z7 and Z8 is a neutral carbene carbon, the other one of Z7 and Z8 is anionic carbon. In some embodiments, at least one of L1, L2, and L3 is not a direct bond. In some embodiments, L2 is a direct bond. In some embodiments, each of L1, L2, and L3 is not a direct bond when they are present. In some embodiments, the rings A, B, and C are each independently selected from the group consisting of phenyl, pyridine, imidazole, and imidazole derived carbene. In some embodiments, the compound has at least one Pt-carbene bond.
In some embodiments of the compound, the compound is selected from the group consisting of:
wherein RD to RG have same definition as RA to RC;
wherein X1 to X25 are each independently carbon or nitrogen; and
wherein R1′, R2′, R3′, and R4′ have the same definition as R1 and R2.
In some embodiments of the compound, the compound is selected from groups consisting of:
According to another aspect, an organic light emitting device (OLED) is disclosed where the OLED comprises: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, the organic layer comprising a compound comprising a first ligand LA Selected from the group consisting of:
wherein ring A is a 5- or 6-membered carbocyclic or heterocyclic ring; wherein Z to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus; wherein Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron; wherein R1, R2, and RA each independently represents none to a maximum possible number of substitutions; wherein each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two substitutions in R1, R2, and RA are optionally joined or fused into a ring; wherein the ligand LA is coordinated to a metal M; wherein if LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; wherein if LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and wherein M is optionally coordinated to other ligands.
In some embodiments of the OLED, each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.
A consumer product comprising the OLED is also disclosed.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
An emissive region in an OLED is also disclosed. The emissive region comprising a compound having a first ligand LA selected from the group consisting of:
wherein ring A is a 5- or 6-membered carbocyclic or heterocyclic ring; wherein Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus; wherein Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron; wherein R1, R2, and RA each independently represents none to a maximum possible number of substitutions; wherein each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two substitutions in R1, R2, and RA are optionally joined or fused into a ring; wherein the ligand LA is coordinated to a metal M; wherein if LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; wherein if LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and wherein M is optionally coordinated to other ligands.
In some embodiments of the emissive region, the compound is an emissive dopant or a non-emissive dopant. In some embodiments, the emissive region further comprises a host, wherein the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
In some embodiments, the emissive region further comprises a host, wherein the host is selected from the group consisting of:
and combinations thereof.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used may be a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example a Zn containing inorganic material e.g. ZnS.
The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the group consisting of:
and combinations thereof.
Additional information on possible hosts is provided below.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
Conductivity Dopants:
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
EBL:
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
Examples of other organic compounds used as host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,
Additional Emitters:
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
Charge Generation Layer (CGL)
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
EXPERIMENTALThe inventive compound (Compound 98) exhibited much deeper blue emission than the Comparative Compound below (458 nm vs. 492 nm), indicating that the inventive compound is suitable for use as a blue emitter in an OLED display, whereas the Comparative Compound is not.
Synthesis of Compound 98
Compound 98 was synthesized in five steps as follows:
2-bromo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole: A mixture of 2-bromo-9H-carbazole (6 g, 24.38 mmol), 3,4-dihydro-2H-pyran (6.67 ml, 73.1 mmol) and pyridinium p-toluenesulfonate (0.306 g, 1.219 mmol) in dichloromethane (100 ml) was refluxed overnight. The reaction mixture was cooled to room temperature, concentrated, and chromatographed on silica (dichloromethane). The product was dried under vacuum. The white sticky paste obtained solidified under vacuum (99% yield).
5-(9-(tetrahydro-2H-pyran-2-yl)-9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole: A mixture of 2-bromo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole (1.5 g, 4.54 mmol), 5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (0.941 g, 4.54 mmol), Pd2Cl2(allyl)2 (0.033 g, 0.091 mmol), di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine (0.128 g, 0.363 mmol), and sodium 2-methylpropan-2-olate (1.091 g, 11.36 mmol) was placed under a nitrogen atmosphere. Toluene (20 ml) was added to the reaction mixture and it was refluxed for 4 hrs. The crude product was filtered through Celite® and chromatographed on silica (20:1 dichloromethane/ethyl acetate) to afford the desired product in 71% yield.
5-(9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole 4-methylbenzenesulfonate: Pyridinium p-toluenesulfonate (0.809 g, 3.22 mmol) and methanesulfonic acid (0.209 ml, 3.22 mmol) were added to a mixture of 5-(9-(tetrahydro-2H-pyran-2-yl)-9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (1.47 g, 3.22 mmol) in chloroform (15 ml) and methanol (15 ml) at room temperature and heated to 60° C. overnight. The reaction mixture was concentrated to dryness, the product was stirred in deionized water for 1 h, and isolated in 86% yield by filtration.
5-(9-(3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenyl)-9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole: A mixture of 1-(3-chlorophenyl)-4-(2,6-diisopropylphenyl)-1H-pyrazole (300 mg, 0.885 mmol), 5-(9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole 4-methylbenzenesulfonate (482 mg, 0.885 mmol), Pd2Cl2(allyl)2 (9.72 mg, 0.027 mmol), di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine (37.4 mg, 0.106 mmol), and sodium 2-methylpropan-2-olate (298 mg, 3.10 mmol) was placed under a nitrogen atmosphere. Toluene (6 ml) was added, and the reaction mixture was refluxed for 1 hr. The reaction mixture was cooled to room temperature, filtered through Celite®, and chromatographed on silica (dichloromethane to 30:1 dichloromethane/ethyl acetate) to afford the desired product in 90% yield.
Compound 98: A mixture of 5-(9-(3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenyl)-9H-carbazol-2-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (560 mg, 0.830 mmol) and K2PtCl4 (344 mg, 0.830 mmol) in a Schlenk tube was placed under a nitrogen atmosphere. Acetic Acid (40 ml) was added and the reaction mixture refluxed for 2 days. The reaction mixture was then cooled to room temperature and water added. The resulting solid was collected by filtration, dissolved in dichloromethane, and dried over MgSO4. Chromatography on silica (1:1 dichloromethane/heptane) followed by trituration in MeOH and drying afforded the desired compound in 18% yield.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
Claims
1. A compound comprising a first ligand LA selected from the group consisting of:
- wherein ring A is a 5- or 6-membered carbocyclic or heterocyclic ring;
- wherein Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus;
- wherein Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron;
- wherein each R1, R2, and RA each independently represents none to a maximum possible number of substitutions;
- wherein each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
- wherein any two substitutions in R1, R2, and RA are optionally joined or fused into a ring;
- wherein the ligand LA is coordinated to an Ir atom;
- wherein if LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- wherein if LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
- wherein the Ir can be coordinated to other ligands.
2. The compound of claim 1, wherein each R1, R2, and RA is independently selected from hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.
3. The compound of claim 1, wherein Z1 is an anionic coordinating atom selected from the group consisting of C, N, and O.
4. The compound of claim 3, wherein the anionic coordinating carbon is an sp2 carbon atom of a ring selected from the group consisting of benzene, pyridine, furan, thiophene, and pyrrole;
- wherein the anionic coordinating nitrogen is an sp2 nitrogen atom of an N-heterocyclic ring selected from the group consisting of imidazole, benzoimidazole, pyrazole, and triazole; and
- wherein the anionic oxygen atom is the oxygen atom from a carboxylic acid or ether.
5. The compound of claim 1, wherein Z1 is a neutral coordinating atom selected from the group consisting of C, P, and N.
6. The compound of claim 5, wherein the neutral carbon is the neutral carbene carbon of an N-heterocyclic carbene;
- wherein the neutral phosphorus is the phosphorus atom of a trisubstituted phosphine; and
- wherein the neutral nitrogen is an sp2 nitrogen atom of an N-heterocyclic ring selected from the group consisting of pyridine, imidazole, benzoimidazole, pyrazole, and triazole.
7. The compound of claim 1, wherein Z6 is CRR′, PR, or BR;
- wherein R and R′ are independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and
- wherein any adjacent substitutions in R and R′ are optionally joined or fused into a ring.
8. The compound of claim 1, wherein the first ligand LA selected from the group consisting of:
- wherein R1′ and R2′ have the same definition as R1 and R2; and
- wherein X1 to X8 are each independently carbon or nitrogen.
9. The compound of claim 1, wherein the first ligand LA is selected from the group consisting of:
- wherein Y is selected from the group consisting of O, S, Se, and NRD;
- wherein X1 to X20 are each independently selected from the group consisting of carbon and nitrogen;
- wherein R1′, R2′, RA′, and RD each independently represents from none to a maximum possible number of substitutions;
- wherein R1′, R2′, RA′, and RD are each independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and wherein any two adjacent substituents are optionally joined to form into a ring.
10. The compound of claim 1, wherein the first ligand LA is selected from the group consisting of:
11. The compound of claim 1, wherein the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other.
12. The compound of claim 11, wherein LB and LC are each independently selected from the group consisting of:
- wherein each Y1 to Y13 are independently selected from the group consisting of carbon and nitrogen;
- wherein Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRfRR, SiReRf, and GeReRf;
- wherein Re and Rf are optionally fused or joined to form a ring;
- wherein each Ra, Rb, Rc, and Rd may independently represent from mono substitution to the maximum possible number of substitution, or no substitution;
- wherein each Ra, Rb, Rc, Rd, Re and Rf is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
- wherein any two adjacent substituents of Ra, Rb, Rc, and Rd are optionally fused or joined to form a ring or form a multidentate ligand.
13. The compound of claim 12, wherein LB and LC are each independently selected from the group consisting of:
14. The compound of claim 11, wherein the compound is selected from the group consisting of Compound Ax having the formula Ir(LAi)2(LCj); in which R3, R4, and R5 are defined as: Ligand R3 R4 R5 LC1 RD1 RD1 H LC2 RD2 RD2 H LC3 RD3 RD3 H LC4 RD4 RD4 H LC5 RD5 RD5 H LC6 RD6 RD6 H LC7 RD7 RD7 H LC8 RD8 RD8 H LC9 RD9 RD9 H LC10 RD10 RD10 H LC11 RD11 RD11 H LC12 RD12 RD12 H LC13 RD13 RD13 H LC14 RD14 RD14 H LC15 RD15 RD15 H LC16 RD16 RD16 H LC17 RD17 RD17 H LC18 RD18 RD18 H LC19 RD19 RD19 H LC20 RD20 RD20 H LC21 RD21 RD21 H LC22 RD22 RD22 H LC23 RD23 RD23 H LC24 RD24 RD24 H LC25 RD25 RD25 H LC26 RD26 RD26 H LC27 RD27 RD27 H LC28 RD28 RD28 H LC29 RD29 RD29 H LC30 RD30 RD30 H LC31 RD31 RD31 H LC32 RD32 RD32 H LC33 RD33 RD33 H LC34 RD34 RD34 H LC35 RD35 RD35 H LC36 RD40 RD40 H LC37 RD41 RD41 H LC38 RD42 RD42 H LC39 RD64 RD64 H LC40 RD66 RD66 H LC41 RD68 RD68 H LC42 RD76 RD76 H LC43 RD1 RD2 H LC44 RD1 RD3 H LC45 RD1 RD4 H LC46 RD1 RD5 H LC47 RD1 RD6 H LC48 RD1 RD7 H LC49 RD1 RD8 H LC50 RD1 RD9 H LC51 RD1 RD10 H LC52 RD1 RD11 H LC53 RD1 RD12 H LC54 RD1 RD13 H LC55 RD1 RD14 H LC56 RD1 RD15 H LC57 RD1 RD16 H LC58 RD1 RD17 H LC59 RD1 RD18 H LC60 RD1 RD19 H LC61 RD1 RD20 H LC62 RD1 RD21 H LC63 RD1 RD22 H LC64 RD1 RD23 H LC65 RD1 RD24 H LC66 RD1 RD25 H LC67 RD1 RD26 H LC68 RD1 RD27 H LC69 RD1 RD28 H LC70 RD1 RD29 H LC71 RD1 RD30 H LC72 RD1 RD31 H LC73 RD1 RD32 H LC74 RD1 RD33 H LC75 RD1 RD34 H LC76 RD1 RD35 H LC77 RD1 RD40 H LC78 RD1 RD41 H LC79 RD1 RD42 H LC80 RD1 RD64 H LC81 RD1 RD66 H LC82 RD1 RD68 H LC83 RD1 RD76 H LC84 RD2 RD1 H LC85 RD2 RD3 H LC86 RD2 RD4 H LC87 RD2 RD5 H LC88 RD2 RD6 H LC89 RD2 RD7 H LC90 RD2 RD8 H LC91 RD2 RD9 H LC92 RD2 RD10 H LC93 RD2 RD11 H LC94 RD2 RD12 H LC95 RD2 RD13 H LC96 RD2 RD14 H LC97 RD2 RD15 H LC98 RD2 RD16 H LC99 RD2 RD17 H LC100 RD2 RD18 H LC101 RD2 RD19 H LC102 RD2 RD20 H LC103 RD2 RD21 H LC104 RD2 RD22 H LC105 RD2 RD23 H LC106 RD2 RD24 H LC107 RD2 RD25 H LC108 RD2 RD26 H LC109 RD2 RD27 H LC110 RD2 RD28 H LC111 RD2 RD29 H LC112 RD2 RD30 H LC113 RD2 RD31 H LC114 RD2 RD32 H LC115 RD2 RD33 H LC116 RD2 RD34 H LC117 RD2 RD35 H LC118 RD2 RD40 H LC119 RD2 RD41 H LC120 RD2 RD42 H LC121 RD2 RD64 H LC122 RD2 RD66 H LC123 RD2 RD68 H LC124 RD2 RD76 H LC125 RD3 RD4 H LC126 RD3 RD5 H LC127 RD3 RD6 H LC128 RD3 RD7 H LC129 RD3 RD8 H LC130 RD3 RD9 H LC131 RD3 RD10 H LC132 RD3 RD11 H LC133 RD3 RD12 H LC134 RD3 RD13 H LC135 RD3 RD14 H LC136 RD3 RD15 H LC137 RD3 RD16 H LC138 RD3 RD17 H LC139 RD3 RD18 H LC140 RD3 RD19 H LC141 RD3 RD20 H LC142 RD3 RD21 H LC143 RD3 RD22 H LC144 RD3 RD23 H LC145 RD3 RD24 H LC146 RD3 RD25 H LC147 RD3 RD26 H LC148 RD3 RD27 H LC149 RD3 RD28 H LC150 RD3 RD29 H LC151 RD3 RD30 H LC152 RD3 RD31 H LC153 RD3 RD32 H LC154 RD3 RD33 H LC155 RD3 RD34 H LC156 RD3 RD35 H LC157 RD3 RD40 H LC158 RD3 RD41 H LC159 RD3 RD42 H LC160 RD3 RD64 H LC161 RD3 RD66 H LC162 RD3 RD68 H LC163 RD3 RD76 H LC164 RD4 RD5 H LC165 RD4 RD6 H LC166 RD4 RD7 H LC167 RD4 RD8 H LC168 RD4 RD9 H LC169 RD4 RD10 H LC170 RD4 RD11 H LC171 RD4 RD12 H LC172 RD4 RD13 H LC173 RD4 RD14 H LC174 RD4 RD15 H LC175 RD4 RD16 H LC176 RD4 RD17 H LC177 RD4 RD18 H LC178 RD4 RD19 H LC179 RD4 RD20 H LC180 RD4 RD21 H LC181 RD4 RD22 H LC182 RD4 RD23 H LC183 RD4 RD24 H LC184 RD4 RD25 H LC185 RD4 RD26 H LC186 RD4 RD27 H LC187 RD4 RD28 H LC188 RD4 RD29 H LC189 RD4 RD30 H LC190 RD4 RD31 H LC191 RD4 RD32 H LC192 RD4 RD33 H LC193 RD4 RD34 H LC194 RD4 RD35 H LC195 RD4 RD40 H LC196 RD4 RD41 H LC197 RD4 RD42 H LC198 RD4 RD64 H LC199 RD4 RD66 H LC200 RD4 RD68 H LC201 RD4 RD76 H LC202 RD4 RD1 H LC203 RD7 RD5 H LC204 RD7 RD6 H LC205 RD7 RD8 H LC206 RD7 RD9 H LC207 RD7 RD10 H LC208 RD7 RD11 H LC209 RD7 RD12 H LC210 RD7 RD13 H LC211 RD7 RD14 H LC212 RD7 RD15 H LC213 RD7 RD16 H LC214 RD7 RD17 H LC215 RD7 RD18 H LC216 RD7 RD19 H LC217 RD7 RD20 H LC218 RD7 RD21 H LC219 RD7 RD22 H LC220 RD7 RD23 H LC221 RD7 RD24 H LC222 RD7 RD25 H LC223 RD7 RD26 H LC224 RD7 RD27 H LC225 RD7 RD28 H LC226 RD7 RD29 H LC227 RD7 RD30 H LC228 RD7 RD31 H LC229 RD7 RD32 H LC230 RD7 RD33 H LC231 RD7 RD34 H LC232 RD7 RD35 H LC233 RD7 RD40 H LC234 RD7 RD41 H LC235 RD7 RD42 H LC236 RD7 RD64 H LC237 RD7 RD66 H LC238 RD7 RD68 H LC239 RD7 RD76 H LC240 RD8 RD5 H LC241 RD8 RD6 H LC242 RD8 RD9 H LC243 RD8 RD10 H LC244 RD8 RD11 H LC245 RD8 RD12 H LC246 RD8 RD13 H LC247 RD8 RD14 H LC248 RD8 RD15 H LC249 RD8 RD16 H LC250 RD8 RD17 H LC251 RD8 RD18 H LC252 RD8 RD19 H LC253 RD8 RD20 H LC254 RD8 RD21 H LC255 RD8 RD22 H LC256 RD8 RD23 H LC257 RD8 RD24 H LC258 RD8 RD25 H LC259 RD8 RD26 H LC260 RD8 RD27 H LC261 RD8 RD28 H LC262 RD8 RD29 H LC263 RD8 RD30 H LC264 RD8 RD31 H LC265 RD8 RD32 H LC266 RD8 RD33 H LC267 RD8 RD34 H LC268 RD8 RD35 H LC269 RD8 RD40 H LC270 RD8 RD41 H LC271 RD8 RD42 H LC272 RD8 RD64 H LC273 RD8 RD66 H LC274 RD8 RD68 H LC275 RD8 RD76 H LC276 RD11 RD5 H LC277 RD11 RD6 H LC278 RD11 RD9 H LC279 RD11 RD10 H LC280 RD11 RD12 H LC281 RD11 RD13 H LC282 RD11 RD14 H LC283 RD11 RD15 H LC284 RD11 RD16 H LC285 RD11 RD17 H LC286 RD11 RD18 H LC287 RD11 RD19 H LC288 RD11 RD20 H LC289 RD11 RD21 H LC290 RD11 RD22 H LC291 RD11 RD23 H LC292 RD11 RD24 H LC293 RD11 RD25 H LC294 RD11 RD26 H LC295 RD11 RD27 H LC296 RD11 RD28 H LC297 RD11 RD29 H LC298 RD11 RD30 H LC299 RD11 RD31 H LC300 RD11 RD32 H LC301 RD11 RD33 H LC302 RD11 RD34 H LC303 RD11 RD35 H LC304 RD11 RD40 H LC305 RD11 RD41 H LC306 RD11 RD42 H LC307 RD11 RD64 H LC308 RD11 RD66 H LC309 RD11 RD68 H LC310 RD11 RD76 H LC311 RD13 RD5 H LC312 RD13 RD6 H LC313 RD13 RD9 H LC314 RD13 RD10 H LC315 RD13 RD12 H LC316 RD13 RD14 H LC317 RD13 RD15 H LC318 RD13 RD16 H LC319 RD13 RD17 H LC320 RD13 RD18 H LC321 RD13 RD19 H LC322 RD13 RD20 H LC323 RD13 RD21 H LC324 RD13 RD22 H LC325 RD13 RD23 H LC326 RD13 RD24 H LC327 RD13 RD25 H LC328 RD13 RD26 H LC329 RD13 RD27 H LC330 RD13 RD28 H LC331 RD13 RD29 H LC332 RD13 RD30 H LC333 RD13 RD31 H LC334 RD13 RD32 H LC335 RD13 RD33 H LC336 RD13 RD34 H LC337 RD13 RD35 H LC338 RD13 RD40 H LC339 RD13 RD41 H LC340 RD13 RD42 H LC341 RD13 RD64 H LC342 RD13 RD66 H LC343 RD13 RD68 H LC344 RD13 RD76 H LC345 RD14 RD5 H LC346 RD14 RD6 H LC347 RD14 RD9 H LC348 RD14 RD10 H LC349 RD14 RD12 H LC350 RD14 RD15 H LC351 RD14 RD16 H LC352 RD14 RD17 H LC353 RD14 RD18 H LC354 RD14 RD19 H LC355 RD14 RD20 H LC356 RD14 RD21 H LC357 RD14 RD22 H LC358 RD14 RD23 H LC359 RD14 RD24 H LC360 RD14 RD25 H LC361 RD14 RD26 H LC362 RD14 RD27 H LC363 RD14 RD28 H LC364 RD14 RD29 H LC365 RD14 RD30 H LC366 RD14 RD31 H LC367 RD14 RD32 H LC368 RD14 RD33 H LC369 RD14 RD34 H LC370 RD14 RD35 H LC371 RD14 RD40 H LC372 RD14 RD41 H LC373 RD14 RD42 H LC374 RD14 RD64 H LC375 RD14 RD66 H LC376 RD14 RD68 H LC377 RD14 RD76 H LC378 RD22 RD5 H LC379 RD22 RD6 H LC380 RD22 RD9 H LC381 RD22 RD10 H LC382 RD22 RD12 H LC383 RD22 RD15 H LC384 RD22 RD16 H LC385 RD22 RD17 H LC386 RD22 RD18 H LC387 RD22 RD19 H LC388 RD22 RD20 H LC389 RD22 RD21 H LC390 RD22 RD23 H LC391 RD22 RD24 H LC392 RD22 RD25 H LC393 RD22 RD26 H LC394 RD22 RD27 H LC395 RD22 RD28 H LC396 RD22 RD29 H LC397 RD22 RD30 H LC398 RD22 RD31 H LC399 RD22 RD32 H LC400 RD22 RD33 H LC401 RD22 RD34 H LC402 RD22 RD35 H LC403 RD22 RD40 H LC404 RD22 RD41 H LC405 RD22 RD42 H LC406 RD22 RD64 H LC407 RD22 RD66 H LC408 RD22 RD68 H LC409 RD22 RD76 H LC410 RD26 RD5 H LC411 RD26 RD6 H LC412 RD26 RD9 H LC413 RD26 RD10 H LC414 RD26 RD12 H LC415 RD26 RD15 H LC416 RD26 RD16 H LC417 RD26 RD17 H LC418 RD26 RD18 H LC419 RD26 RD19 H LC420 RD26 RD20 H LC421 RD26 RD21 H LC422 RD26 RD23 H LC423 RD26 RD24 H LC424 RD26 RD25 H LC425 RD26 RD27 H LC426 RD26 RD28 H LC427 RD26 RD29 H LC428 RD26 RD30 H LC429 RD26 RD31 H LC430 RD26 RD32 H LC431 RD26 RD33 H LC432 RD26 RD34 H LC433 RD26 RD35 H LC434 RD26 RD40 H LC435 RD26 RD41 H LC436 RD26 RD42 H LC437 RD26 RD64 H LC438 RD26 RD66 H LC439 RD26 RD68 H LC440 RD26 RD76 H LC441 RD35 RD5 H LC442 RD35 RD6 H LC443 RD35 RD9 H LC444 RD35 RD10 H LC445 RD35 RD12 H LC446 RD35 RD15 H LC447 RD35 RD16 H LC448 RD35 RD17 H LC449 RD35 RD18 H LC450 RD35 RD19 H LC451 RD35 RD20 H LC452 RD35 RD21 H LC453 RD35 RD23 H LC454 RD35 RD24 H LC455 RD35 RD25 H LC456 RD35 RD27 H LC457 RD35 RD28 H LC458 RD35 RD29 H LC459 RD35 RD30 H LC460 RD35 RD31 H LC461 RD35 RD32 H LC462 RD35 RD33 H LC463 RD35 RD34 H LC464 RD35 RD40 H LC465 RD35 RD41 H LC466 RD35 RD42 H LC467 RD35 RD64 H LC468 RD35 RD66 H LC469 RD35 RD68 H LC470 RD35 RD76 H LC471 RD40 RD5 H LC472 RD40 RD6 H LC473 RD40 RD9 H LC474 RD40 RD10 H LC475 RD40 RD12 H LC476 RD40 RD15 H LC477 RD40 RD16 H LC478 RD40 RD17 H LC479 RD40 RD18 H LC480 RD40 RD19 H LC481 RD40 RD20 H LC482 RD40 RD21 H LC483 RD40 RD23 H LC484 RD40 RD24 H LC485 RD40 RD25 H LC486 RD40 RD27 H LC487 RD40 RD28 H LC488 RD40 RD29 H LC489 RD40 RD30 H LC490 RD40 RD31 H LC491 RD40 RD32 H LC492 RD40 RD33 H LC493 RD40 RD34 H LC494 RD40 RD41 H LC495 RD40 RD42 H LC496 RD40 RD64 H LC497 RD40 RD66 H LC498 RD40 RD68 H LC499 RD40 RD76 H LC500 RD41 RD5 H LC501 RD41 RD6 H LC502 RD41 RD9 H LC503 RD41 RD10 H LC504 RD41 RD12 H LC505 RD41 RD15 H LC506 RD41 RD16 H LC507 RD41 RD17 H LC508 RD41 RD18 H LC509 RD41 RD19 H LC510 RD41 RD20 H LC511 RD41 RD21 H LC512 RD41 RD23 H LC513 RD41 RD24 H LC514 RD41 RD25 H LC515 RD41 RD27 H LC516 RD41 RD28 H LC517 RD41 RD29 H LC518 RD41 RD30 H LC519 RD41 RD31 H LC520 RD41 RD32 H LC521 RD41 RD33 H LC522 RD41 RD34 H LC523 RD41 RD42 H LC524 RD41 RD64 H LC525 RD41 RD66 H LC526 RD41 RD68 H LC527 RD41 RD76 H LC528 RD64 RD5 H LC529 RD64 RD6 H LC530 RD64 RD9 H LC531 RD64 RD10 H LC532 RD64 RD12 H LC533 RD64 RD15 H LC534 RD64 RD16 H LC535 RD64 RD17 H LC536 RD64 RD18 H LC537 RD64 RD19 H LC538 RD64 RD20 H LC539 RD64 RD21 H LC540 RD64 RD23 H LC541 RD64 RD24 H LC542 RD64 RD25 H LC543 RD64 RD27 H LC544 RD64 RD28 H LC545 RD64 RD29 H LC546 RD64 RD30 H LC547 RD64 RD31 H LC548 RD64 RD32 H LC549 RD64 RD33 H LC550 RD64 RD34 H LC551 RD64 RD42 H LC552 RD64 RD64 H LC553 RD64 RD66 H LC554 RD64 RD68 H LC555 RD64 RD76 H LC556 RD66 RD5 H LC557 RD66 RD6 H LC558 RD66 RD9 H LC559 RD66 RD10 H LC560 RD66 RD12 H LC561 RD66 RD15 H LC562 RD66 RD16 H LC563 RD66 RD17 H LC564 RD66 RD18 H LC565 RD66 RD19 H LC566 RD66 RD20 H LC567 RD66 RD21 H LC568 RD66 RD23 H LC569 RD66 RD24 H LC570 RD66 RD25 H LC571 RD66 RD27 H LC572 RD66 RD28 H LC573 RD66 RD29 H LC574 RD66 RD30 H LC575 RD66 RD31 H LC576 RD66 RD32 H LC577 RD66 RD33 H LC578 RD66 RD34 H LC579 RD66 RD42 H LC580 RD66 RD68 H LC581 RD66 RD76 H LC582 RD68 RD5 H LC583 RD68 RD6 H LC584 RD68 RD9 H LC585 RD68 RD10 H LC586 RD68 RD12 H LC587 RD68 RD15 H LC588 RD68 RD16 H LC589 RD68 RD17 H LC590 RD68 RD18 H LC591 RD68 RD19 H LC592 RD68 RD20 H LC593 RD68 RD21 H LC594 RD68 RD23 H LC595 RD68 RD24 H LC596 RD68 RD25 H LC597 RD68 RD27 H LC598 RD68 RD28 H LC599 RD68 RD29 H LC600 RD68 RD30 H LC601 RD68 RD31 H LC602 RD68 RD32 H LC603 RD68 RD33 H LC604 RD68 RD34 H LC605 RD68 RD42 H LC606 RD68 RD76 H LC607 RD76 RD5 H LC608 RD76 RD6 H LC609 RD76 RD9 H LC610 RD76 RD10 H LC611 RD76 RD12 H LC612 RD76 RD15 H LC613 RD76 RD16 H LC614 RD76 RD17 H LC615 RD76 RD18 H LC616 RD76 RD19 H LC617 RD76 RD20 H LC618 RD76 RD21 H LC619 RD76 RD23 H LC620 RD76 RD24 H LC621 RD76 RD25 H LC622 RD76 RD27 H LC623 RD76 RD28 H LC624 RD76 RD29 H LC625 RD76 RD30 H LC626 RD76 RD31 H LC627 RD76 RD32 H LC628 RD76 RD33 H LC629 RD76 RD34 H LC630 RD76 RD42 H LC631 RD1 RD1 RD1 LC632 RD2 RD2 RD1 LC633 RD3 RD3 RD1 LC634 RD4 RD4 RD1 LC635 RD5 RD5 RD1 LC636 RD6 RD6 RD1 LC637 RD7 RD7 RD1 LC638 RD8 RD8 RD1 LC639 RD9 RD9 RD1 LC640 RD10 RD10 RD1 LC641 RD11 RD11 RD1 LC642 RD12 RD12 RD1 LC643 RD13 RD13 RD1 LC644 RD14 RD14 RD1 LC645 RD15 RD15 RD1 LC646 RD16 RD16 RD1 LC647 RD17 RD17 RD1 LC648 RD18 RD18 RD1 LC649 RD19 RD19 RD1 LC650 RD20 RD20 RD1 LC651 RD21 RD21 RD1 LC652 RD22 RD22 RD1 LC653 RD23 RD23 RD1 LC654 RD24 RD24 RD1 LC655 RD25 RD25 RD1 LC656 RD26 RD26 RD1 LC657 RD27 RD27 RD1 LC658 RD28 RD28 RD1 LC659 RD29 RD29 RD1 LC660 RD30 RD30 RD1 LC661 RD31 RD31 RD1 LC662 RD32 RD32 RD1 LC663 RD33 RD33 RD1 LC664 RD34 RD34 RD1 LC665 RD35 RD35 RD1 LC666 RD40 RD40 RD1 LC667 RD41 RD41 RD1 LC668 RD42 RD42 RD1 LC669 RD64 RD64 RD1 LC670 RD66 RD66 RD1 LC671 RD68 RD68 RD1 LC672 RD76 RD76 RD1 LC673 RD1 RD2 RD1 LC674 RD1 RD3 RD1 LC675 RD1 RD4 RD1 LC676 RD1 RD5 RD1 LC677 RD1 RD6 RD1 LC678 RD1 RD7 RD1 LC679 RD1 RD8 RD1 LC680 RD1 RD9 RD1 LC681 RD1 RD10 RD1 LC682 RD1 RD11 RD1 LC683 RD1 RD12 RD1 LC684 RD1 RD13 RD1 LC685 RD1 RD14 RD1 LC686 RD1 RD15 RD1 LC687 RD1 RD16 RD1 LC688 RD1 RD17 RD1 LC689 RD1 RD18 RD1 LC690 RD1 RD19 RD1 LC691 RD1 RD20 RD1 LC692 RD1 RD21 RD1 LC693 RD1 RD22 RD1 LC694 RD1 RD23 RD1 LC695 RD1 RD24 RD1 LC696 RD1 RD25 RD1 LC697 RD1 RD26 RD1 LC698 RD1 RD27 RD1 LC699 RD1 RD28 RD1 LC700 RD1 RD29 RD1 LC701 RD1 RD30 RD1 LC702 RD1 RD31 RD1 LC703 RD1 RD32 RD1 LC704 RD1 RD33 RD1 LC705 RD1 RD34 RD1 LC706 RD1 RD35 RD1 LC707 RD1 RD40 RD1 LC708 RD1 RD41 RD1 LC709 RD1 RD42 RD1 LC710 RD1 RD64 RD1 LC711 RD1 RD66 RD1 LC712 RD1 RD68 RD1 LC713 RD1 RD76 RD1 LC714 RD2 RD1 RD1 LC715 RD2 RD3 RD1 LC716 RD2 RD4 RD1 LC717 RD2 RD5 RD1 LC718 RD2 RD6 RD1 LC719 RD2 RD7 RD1 LC720 RD2 RD8 RD1 LC721 RD2 RD9 RD1 LC722 RD2 RD10 RD1 LC723 RD2 RD11 RD1 LC724 RD2 RD12 RD1 LC725 RD2 RD13 RD1 LC726 RD2 RD14 RD1 LC727 RD2 RD15 RD1 LC728 RD2 RD16 RD1 LC729 RD2 RD17 RD1 LC730 RD2 RD18 RD1 LC731 RD2 RD19 RD1 LC732 RD2 RD20 RD1 LC733 RD2 RD21 RD1 LC734 RD2 RD22 RD1 LC735 RD2 RD23 RD1 LC736 RD2 RD24 RD1 LC737 RD2 RD25 RD1 LC738 RD2 RD26 RD1 LC739 RD2 RD27 RD1 LC740 RD2 RD28 RD1 LC741 RD2 RD29 RD1 LC742 RD2 RD30 RD1 LC743 RD2 RD31 RD1 LC744 RD2 RD32 RD1 LC745 RD2 RD33 RD1 LC746 RD2 RD34 RD1 LC747 RD2 RD35 RD1 LC748 RD2 RD40 RD1 LC749 RD2 RD41 RD1 LC750 RD2 RD42 RD1 LC751 RD2 RD64 RD1 LC752 RD2 RD66 RD1 LC753 RD2 RD68 RD1 LC754 RD2 RD76 RD1 LC755 RD3 RD4 RD1 LC756 RD3 RD5 RD1 LC757 RD3 RD6 RD1 LC758 RD3 RD7 RD1 LC759 RD3 RD8 RD1 LC760 RD3 RD9 RD1 LC761 RD3 RD10 RD1 LC762 RD3 RD11 RD1 LC763 RD3 RD12 RD1 LC764 RD3 RD13 RD1 LC765 RD3 RD14 RD1 LC766 RD3 RD15 RD1 LC767 RD3 RD16 RD1 LC768 RD3 RD17 RD1 LC769 RD3 RD18 RD1 LC770 RD3 RD19 RD1 LC771 RD3 RD20 RD1 LC772 RD3 RD21 RD1 LC773 RD3 RD22 RD1 LC774 RD3 RD23 RD1 LC775 RD3 RD24 RD1 LC776 RD3 RD25 RD1 LC777 RD3 RD26 RD1 LC778 RD3 RD27 RD1 LC779 RD3 RD28 RD1 LC780 RD3 RD29 RD1 LC781 RD3 RD30 RD1 LC782 RD3 RD31 RD1 LC783 RD3 RD32 RD1 LC784 RD3 RD33 RD1 LC785 RD3 RD34 RD1 LC786 RD3 RD35 RD1 LC787 RD3 RD40 RD1 LC788 RD3 RD41 RD1 LC789 RD3 RD42 RD1 LC790 RD3 RD64 RD1 LC791 RD3 RD66 RD1 LC792 RD3 RD68 RD1 LC793 RD3 RD76 RD1 LC794 RD4 RD5 RD1 LC795 RD4 RD6 RD1 LC796 RD4 RD7 RD1 LC797 RD4 RD8 RD1 LC798 RD4 RD9 RD1 LC799 RD4 RD10 RD1 LC800 RD4 RD11 RD1 LC801 RD4 RD12 RD1 LC802 RD4 RD13 RD1 LC803 RD4 RD14 RD1 LC804 RD4 RD15 RD1 LC805 RD4 RD16 RD1 LC806 RD4 RD17 RD1 LC807 RD4 RD18 RD1 LC808 RD4 RD19 RD1 LC809 RD4 RD20 RD1 LC810 RD4 RD21 RD1 LC811 RD4 RD22 RD1 LC812 RD4 RD23 RD1 LC813 RD4 RD24 RD1 LC814 RD4 RD25 RD1 LC815 RD4 RD26 RD1 LC816 RD4 RD27 RD1 LC817 RD4 RD28 RD1 LC818 RD4 RD29 RD1 LC819 RD4 RD30 RD1 LC820 RD4 RD31 RD1 LC821 RD4 RD32 RD1 LC822 RD4 RD33 RD1 LC823 RD4 RD34 RD1 LC824 RD4 RD35 RD1 LC825 RD4 RD40 RD1 LC826 RD4 RD41 RD1 LC827 RD4 RD42 RD1 LC828 RD4 RD64 RD1 LC829 RD4 RD66 RD1 LC830 RD4 RD68 RD1 LC831 RD4 RD76 RD1 LC832 RD4 RD1 RD1 LC833 RD7 RD5 RD1 LC834 RD7 RD6 RD1 LC835 RD7 RD8 RD1 LC836 RD7 RD9 RD1 LC837 RD7 RD10 RD1 LC838 RD7 RD11 RD1 LC839 RD7 RD12 RD1 LC840 RD7 RD13 RD1 LC841 RD7 RD14 RD1 LC842 RD7 RD15 RD1 LC843 RD7 RD16 RD1 LC844 RD7 RD17 RD1 LC845 RD7 RD18 RD1 LC846 RD7 RD19 RD1 LC847 RD7 RD20 RD1 LC848 RD7 RD21 RD1 LC849 RD7 RD22 RD1 LC850 RD7 RD23 RD1 LC851 RD7 RD24 RD1 LC852 RD7 RD25 RD1 LC853 RD7 RD26 RD1 LC854 RD7 RD27 RD1 LC855 RD7 RD28 RD1 LC856 RD7 RD29 RD1 LC857 RD7 RD30 RD1 LC858 RD7 RD31 RD1 LC859 RD7 RD32 RD1 LC860 RD7 RD33 RD1 LC861 RD7 RD34 RD1 LC862 RD7 RD35 RD1 LC863 RD7 RD40 RD1 LC864 RD7 RD41 RD1 LC865 RD7 RD42 RD1 LC866 RD7 RD64 RD1 LC867 RD7 RD66 RD1 LC868 RD7 RD68 RD1 LC869 RD7 RD76 RD1 LC870 RD8 RD5 RD1 LC871 RD8 RD6 RD1 LC872 RD8 RD9 RD1 LC873 RD8 RD10 RD1 LC874 RD8 RD11 RD1 LC875 RD8 RD12 RD1 LC876 RD8 RD13 RD1 LC877 RD8 RD14 RD1 LC878 RD8 RD15 RD1 LC879 RD8 RD16 RD1 LC880 RD8 RD17 RD1 LC881 RD8 RD18 RD1 LC882 RD8 RD19 RD1 LC883 RD8 RD20 RD1 LC884 RD8 RD21 RD1 LC885 RD8 RD22 RD1 LC886 RD8 RD23 RD1 LC887 RD8 RD24 RD1 LC888 RD8 RD25 RD1 LC889 RD8 RD26 RD1 LC890 RD8 RD27 RD1 LC891 RD8 RD28 RD1 LC892 RD8 RD29 RD1 LC893 RD8 RD30 RD1 LC894 RD8 RD31 RD1 LC895 RD8 RD32 RD1 LC896 RD8 RD33 RD1 LC897 RD8 RD34 RD1 LC898 RD8 RD35 RD1 LC899 RD8 RD40 RD1 LC900 RD8 RD41 RD1 LC901 RD8 RD42 RD1 LC902 RD8 RD64 RD1 LC903 RD8 RD66 RD1 LC904 RD8 RD68 RD1 LC905 RD8 RD76 RD1 LC906 RD11 RD5 RD1 LC907 RD11 RD6 RD1 LC908 RD11 RD9 RD1 LC909 RD11 RD10 RD1 LC910 RD11 RD12 RD1 LC911 RD11 RD13 RD1 LC912 RD11 RD14 RD1 LC913 RD11 RD15 RD1 LC914 RD11 RD16 RD1 LC915 RD11 RD17 RD1 LC916 RD11 RD18 RD1 LC917 RD11 RD19 RD1 LC918 RD11 RD20 RD1 LC919 RD11 RD21 RD1 LC920 RD11 RD22 RD1 LC921 RD11 RD23 RD1 LC922 RD11 RD24 RD1 LC923 RD11 RD25 RD1 LC924 RD11 RD26 RD1 LC925 RD11 RD27 RD1 LC926 RD11 RD28 RD1 LC927 RD11 RD29 RD1 LC928 RD11 RD30 RD1 LC929 RD11 RD31 RD1 LC930 RD11 RD32 RD1 LC931 RD11 RD33 RD1 LC932 RD11 RD34 RD1 LC933 RD11 RD35 RD1 LC934 RD11 RD40 RD1 LC935 RD11 RD41 RD1 LC936 RD11 RD42 RD1 LC937 RD11 RD64 RD1 LC938 RD11 RD66 RD1 LC939 RD11 RD68 RD1 LC940 RD11 RD76 RD1 LC941 RD13 RD5 RD1 LC942 RD13 RD6 RD1 LC943 RD13 RD9 RD1 LC944 RD13 RD10 RD1 LC945 RD13 RD12 RD1 LC946 RD13 RD14 RD1 LC947 RD13 RD15 RD1 LC948 RD13 RD16 RD1 LC949 RD13 RD17 RD1 LC950 RD13 RD18 RD1 LC951 RD13 RD19 RD1 LC952 RD13 RD20 RD1 LC953 RD13 RD21 RD1 LC954 RD13 RD22 RD1 LC955 RD13 RD23 RD1 LC956 RD13 RD24 RD1 LC957 RD13 RD25 RD1 LC958 RD13 RD26 RD1 LC959 RD13 RD27 RD1 LC960 RD13 RD28 RD1 LC961 RD13 RD29 RD1 LC962 RD13 RD30 RD1 LC963 RD13 RD31 RD1 LC964 RD13 RD32 RD1 LC965 RD13 RD33 RD1 LC966 RD13 RD34 RD1 LC967 RD13 RD35 RD1 LC968 RD13 RD40 RD1 LC969 RD13 RD41 RD1 LC970 RD13 RD42 RD1 LC971 RD13 RD64 RD1 LC972 RD13 RD66 RD1 LC973 RD13 RD68 RD1 LC974 RD13 RD76 RD1 LC975 RD14 RD5 RD1 LC976 RD14 RD6 RD1 LC977 RD14 RD9 RD1 LC978 RD14 RD10 RD1 LC979 RD14 RD12 RD1 LC980 RD14 RD15 RD1 LC981 RD14 RD16 RD1 LC982 RD14 RD17 RD1 LC983 RD14 RD18 RD1 LC984 RD14 RD19 RD1 LC985 RD14 RD20 RD1 LC986 RD14 RD21 RD1 LC987 RD14 RD22 RD1 LC988 RD14 RD23 RD1 LC989 RD14 RD24 RD1 LC990 RD14 RD25 RD1 LC991 RD14 RD26 RD1 LC992 RD14 RD27 RD1 LC993 RD14 RD28 RD1 LC994 RD14 RD29 RD1 LC995 RD14 RD30 RD1 LC996 RD14 RD31 RD1 LC997 RD14 RD32 RD1 LC998 RD14 RD33 RD1 LC999 RD14 RD34 RD1 LC1000 RD14 RD35 RD1 LC1001 RD14 RD40 RD1 LC1002 RD14 RD41 RD1 LC1003 RD14 RD42 RD1 LC1004 RD14 RD64 RD1 LC1005 RD14 RD66 RD1 LC1006 RD14 RD68 RD1 LC1007 RD14 RD76 RD1 LC1008 RD22 RD5 RD1 LC1009 RD22 RD6 RD1 LC1010 RD22 RD9 RD1 LC1011 RD22 RD10 RD1 LC1012 RD22 RD12 RD1 LC1013 RD22 RD15 RD1 LC1014 RD22 RD16 RD1 LC1015 RD22 RD17 RD1 LC1016 RD22 RD18 RD1 LC1017 RD22 RD19 RD1 LC1018 RD22 RD20 RD1 LC1019 RD22 RD21 RD1 LC1020 RD22 RD23 RD1 LC1021 RD22 RD24 RD1 LC1022 RD22 RD25 RD1 LC1023 RD22 RD26 RD1 LC1024 RD22 RD27 RD1 LC1025 RD22 RD28 RD1 LC1026 RD22 RD29 RD1 LC1027 RD22 RD30 RD1 LC1028 RD22 RD31 RD1 LC1029 RD22 RD32 RD1 LC1030 RD22 RD33 RD1 LC1031 RD22 RD34 RD1 LC1032 RD22 RD35 RD1 LC1033 RD22 RD40 RD1 LC1034 RD22 RD41 RD1 LC1035 RD22 RD42 RD1 LC1036 RD22 RD64 RD1 LC1037 RD22 RD66 RD1 LC1038 RD22 RD68 RD1 LC1039 RD22 RD76 RD1 LC1040 RD26 RD5 RD1 LC1041 RD26 RD6 RD1 LC1042 RD26 RD9 RD1 LC1043 RD26 RD10 RD1 LC1044 RD26 RD12 RD1 LC1045 RD26 RD15 RD1 LC1046 RD26 RD16 RD1 LC1047 RD26 RD17 RD1 LC1048 RD26 RD18 RD1 LC1049 RD26 RD19 RD1 LC1050 RD26 RD20 RD1 LC1051 RD26 RD21 RD1 LC1052 RD26 RD23 RD1 LC1053 RD26 RD24 RD1 LC1054 RD26 RD25 RD1 LC1055 RD26 RD27 RD1 LC1056 RD26 RD28 RD1 LC1057 RD26 RD29 RD1 LC1058 RD26 RD30 RD1 LC1059 RD26 RD31 RD1 LC1060 RD26 RD32 RD1 LC1061 RD26 RD33 RD1 LC1062 RD26 RD34 RD1 LC1063 RD26 RD35 RD1 LC1064 RD26 RD40 RD1 LC1065 RD26 RD41 RD1 LC1066 RD26 RD42 RD1 LC1067 RD26 RD64 RD1 LC1068 RD26 RD66 RD1 LC1069 RD26 RD68 RD1 LC1070 RD26 RD76 RD1 LC1071 RD35 RD5 RD1 LC1072 RD35 RD6 RD1 LC1073 RD35 RD9 RD1 LC1074 RD35 RD10 RD1 LC1075 RD35 RD12 RD1 LC1076 RD35 RD15 RD1 LC1077 RD35 RD16 RD1 LC1078 RD35 RD17 RD1 LC1079 RD35 RD18 RD1 LC1080 RD35 RD19 RD1 LC1081 RD35 RD20 RD1 LC1082 RD35 RD21 RD1 LC1083 RD35 RD23 RD1 LC1084 RD35 RD24 RD1 LC1085 RD35 RD25 RD1 LC1086 RD35 RD27 RD1 LC1087 RD35 RD28 RD1 LC1088 RD35 RD29 RD1 LC1089 RD35 RD30 RD1 LC1090 RD35 RD31 RD1 LC1091 RD35 RD32 RD1 LC1092 RD35 RD33 RD1 LC1093 RD35 RD34 RD1 LC1094 RD35 RD40 RD1 LC1095 RD35 RD41 RD1 LC1096 RD35 RD42 RD1 LC1097 RD35 RD64 RD1 LC1098 RD35 RD66 RD1 LC1099 RD35 RD68 RD1 LC1100 RD35 RD76 RD1 LC1101 RD40 RD5 RD1 LC1102 RD40 RD6 RD1 LC1103 RD40 RD9 RD1 LC1104 RD40 RD10 RD1 LC1105 RD40 RD12 RD1 LC1106 RD40 RD15 RD1 LC1107 RD40 RD16 RD1 LC1108 RD40 RD17 RD1 LC1109 RD40 RD18 RD1 LC1110 RD40 RD19 RD1 LC1111 RD40 RD20 RD1 LC1112 RD40 RD21 RD1 LC1113 RD40 RD23 RD1 LC1114 RD40 RD24 RD1 LC1115 RD40 RD25 RD1 LC1116 RD40 RD27 RD1 LC1117 RD40 RD28 RD1 LC1118 RD40 RD29 RD1 LC1119 RD40 RD30 RD1 LC1120 RD40 RD31 RD1 LC1121 RD40 RD32 RD1 LC1122 RD40 RD33 RD1 LC1123 RD40 RD34 RD1 LC1124 RD40 RD41 RD1 LC1125 RD40 RD42 RD1 LC1126 RD40 RD64 RD1 LC1127 RD40 RD66 RD1 LC1128 RD40 RD68 RD1 LC1129 RD40 RD76 RD1 LC1130 RD41 RD5 RD1 LC1131 RD41 RD6 RD1 LC1132 RD41 RD9 RD1 LC1133 RD41 RD10 RD1 LC1134 RD41 RD12 RD1 LC1135 RD41 RD15 RD1 LC1136 RD41 RD16 RD1 LC1137 RD41 RD17 RD1 LC1138 RD41 RD18 RD1 LC1139 RD41 RD19 RD1 LC1140 RD41 RD20 RD1 LC1141 RD41 RD21 RD1 LC1142 RD41 RD23 RD1 LC1143 RD41 RD24 RD1 LC1144 RD41 RD25 RD1 LC1145 RD41 RD27 RD1 LC1146 RD41 RD28 RD1 LC1147 RD41 RD29 RD1 LC1148 RD41 RD30 RD1 LC1149 RD41 RD31 RD1 LC1150 RD41 RD32 RD1 LC1151 RD41 RD33 RD1 LC1152 RD41 RD34 RD1 LC1153 RD41 RD42 RD1 LC1154 RD41 RD64 RD1 LC1155 RD41 RD66 RD1 LC1156 RD41 RD68 RD1 LC1157 RD41 RD76 RD1 LC1158 RD64 RD5 RD1 LC1159 RD64 RD6 RD1 LC1160 RD64 RD9 RD1 LC1161 RD64 RD10 RD1 LC1162 RD64 RD12 RD1 LC1163 RD64 RD15 RD1 LC1164 RD64 RD16 RD1 LC1165 RD64 RD17 RD1 LC1166 RD64 RD18 RD1 LC1167 RD64 RD19 RD1 LC1168 RD64 RD20 RD1 LC1169 RD64 RD21 RD1 LC1170 RD64 RD23 RD1 LC1171 RD64 RD24 RD1 LC1172 RD64 RD25 RD1 LC1173 RD64 RD27 RD1 LC1174 RD64 RD28 RD1 LC1175 RD64 RD29 RD1 LC1176 RD64 RD30 RD1 LC1177 RD64 RD31 RD1 LC1178 RD64 RD32 RD1 LC1179 RD64 RD33 RD1 LC1180 RD64 RD34 RD1 LC1181 RD64 RD42 RD1 LC1182 RD64 RD64 RD1 LC1183 RD64 RD66 RD1 LC1184 RD64 RD68 RD1 LC1185 RD64 RD76 RD1 LC1186 RD66 RD5 RD1 LC1187 RD66 RD6 RD1 LC1188 RD66 RD9 RD1 LC1189 RD66 RD10 RD1 LC1190 RD66 RD12 RD1 LC1191 RD66 RD15 RD1 LC1192 RD66 RD16 RD1 LC1193 RD66 RD17 RD1 LC1194 RD66 RD18 RD1 LC1195 RD66 RD19 RD1 LC1196 RD66 RD20 RD1 LC1197 RD66 RD21 RD1 LC1198 RD66 RD23 RD1 LC1199 RD66 RD24 RD1 LC1200 RD66 RD25 RD1 LC1201 RD66 RD27 RD1 LC1202 RD66 RD28 RD1 LC1203 RD66 RD29 RD1 LC1204 RD66 RD30 RD1 LC1205 RD66 RD31 RD1 LC1206 RD66 RD32 RD1 LC1207 RD66 RD33 RD1 LC1208 RD66 RD34 RD1 LC1209 RD66 RD42 RD1 LC1210 RD66 RD68 RD1 LC1211 RD66 RD76 RD1 LC1212 RD68 RD5 RD1 LC1213 RD68 RD6 RD1 LC1214 RD68 RD9 RD1 LC1215 RD68 RD10 RD1 LC1216 RD68 RD12 RD1 LC1217 RD68 RD15 RD1 LC1218 RD68 RD16 RD1 LC1219 RD68 RD17 RD1 LC1220 RD68 RD18 RD1 LC1221 RD68 RD19 RD1 LC1222 RD68 RD20 RD1 LC1223 RD68 RD21 RD1 LC1224 RD68 RD23 RD1 LC1225 RD68 RD24 RD1 LC1226 RD68 RD25 RD1 LC1227 RD68 RD27 RD1 LC1228 RD68 RD28 RD1 LC1229 RD68 RD29 RD1 LC1230 RD68 RD30 RD1 LC1231 RD68 RD31 RD1 LC1232 RD68 RD32 RD1 LC1233 RD68 RD33 RD1 LC1234 RD68 RD34 RD1 LC1235 RD68 RD42 RD1 LC1236 RD68 RD76 RD1 LC1237 RD76 RD5 RD1 LC1238 RD76 RD6 RD1 LC1239 RD76 RD9 RD1 LC1240 RD76 RD10 RD1 LC1241 RD76 RD12 RD1 LC1242 RD76 RD15 RD1 LC1243 RD76 RD16 RD1 LC1244 RD76 RD17 RD1 LC1245 RD76 RD18 RD1 LC1246 RD76 RD19 RD1 LC1247 RD76 RD20 RD1 LC1248 RD76 RD21 RD1 LC1249 RD76 RD23 RD1 LC1250 RD76 RD24 RD1 LC1251 RD76 RD25 RD1 LC1252 RD76 RD27 RD1 LC1253 RD76 RD28 RD1 LC1254 RD76 RD29 RD1 LC1255 RD76 RD30 RD1 LC1256 RD76 RD31 RD1 LC1257 RD76 RD32 RD1 LC1258 RD76 RD33 RD1 LC1259 RD76 RD34 RD1 LC1260 RD76 RD42 RD1
- wherein x is an integer defined by x=1260i+j−1260; wherein i is an integer from 1 to 206, and j is an integer from 1 to 1260; and
- wherein LCj is selected from the group consisting of LC1 through LC1260 that are based on a structure of Formula X,
- wherein RD1 to RD81 has the following structures:
15. The compound of claim 11, wherein the compound is selected from the group consisting of Compound By having the formula Ir(LAi)(LBk)2;
- wherein y is an integer defined by y=460+k−460; i is an integer from 1 to 206, and k is an integer from 1 to 460; and
- wherein LBk has the following structures:
16. An organic light emitting device (OLED) comprising:
- an anode;
- a cathode; and
- an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA selected from the group consisting of:
- wherein ring A is a 5- or 6-membered carbocyclic or heterocyclic ring;
- wherein Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus;
- wherein Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron;
- wherein R1, R2, and RA each independently represents none to a maximum possible number of substitutions;
- wherein each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
- wherein any two substitutions in R1, R2, and RA are optionally joined or fused into a ring;
- wherein the ligand LA is coordinated to Ir;
- wherein if LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- wherein if LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
- wherein Ir can be coordinated to other ligands.
17. The OLED of claim 16, wherein the organic layer further comprises a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
18. A consumer product comprising an organic light-emitting device (OLED) comprising:
- an anode;
- a cathode; and
- an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand LA selected from the group consisting of:
- wherein ring A is a 5- or 6-membered carbocyclic or heterocyclic ring;
- wherein Z1 to Z5 are each independently carbon, nitrogen, oxygen, or phosphorus;
- wherein Z6 is selected from the group consisting of carbon, nitrogen, oxygen, sulfur, phosphorus, and boron;
- wherein R1, R2, and RA each independently represents none to a maximum possible number of substitutions;
- wherein each R1, R2, and RA is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
- wherein any two substitutions in R1, R2, and RA are optionally joined or fused into a ring;
- wherein the ligand LA is coordinated to Ir;
- wherein if LA has a formula according to Formula I, it is linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- wherein if LA has a formula according to Formula II or Formula III, it is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
- wherein Ir can be coordinated to other ligands.
19. The consumer product of claim 18, wherein the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video walls comprising multiple displays tiled together, a theater or stadium screen, and a sign.
20. A formulation comprising the compound of claim 1.
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Type: Grant
Filed: Dec 29, 2020
Date of Patent: Feb 28, 2023
Patent Publication Number: 20220119434
Assignee: UNIVERSAL DISPLAY CORPORATION (Ewing, NJ)
Inventors: Hsiao-Fan Chen (Taipei), Chun Lin (Yardley, PA), Jerald Feldman (Wilmington, DE), Zhiqiang Ji (Ewing, NJ), Daniel W. Silverstein (Ewing, NJ)
Primary Examiner: Shane Fang
Application Number: 17/136,429
